Method of setting hair with epoxy resin compositions



May 10, 1966 H. wlLMsMANN ETAL 3,250,632

METHOD OF SETTING HAIR WITH EPOXY RESIN COMPOSITIONS Filed Feb. l5, 1962 UnitedV States Patent O 3,250,682 METHOD F SETTING HAIR WITH EPOXY RESIN COMPOSITIONS Hermann Wilmsmann and Wolfgang Ludwig, Darmstadt,

Germany, assignors to Wella Aktiengesellschaft, Darmstadt, Germany Filed Feb. 15, 1962, Ser. No. 173,482 Claims priority, application Germany, Feb. 22, 1961,

W 29,518 12 Claims. (Cl. 167-87.1)

The present invention rela-tes to a method of maintaining hair in set condition, and more particularly to methods of and compositions for the treatment of hair so that the hair which is thus treated will remain in se-t condition over prolonged periods of time, and even under moist atmospheric conditions.

It is known that human hair by treatment with reducing agents, such `as substituted mercaptans or sultites, with or without subsequent fixing, can be deformed permanently. It is also known .that it is possible to achieve a deformation of the hair'by coating the hair fibers with a film of a natural resin, such as Icelandic moss, quince seeds, iieawort seeds, gum tragacanth, dextrins, agar-agar, cellulose derivatives, sandarac resin, Siam resin, benzene resins and shellac, or artificial resins such as polyvinyl alcohol, polyacrylates, polyvinylacetates, polyethylene glycol, condensation products of urea and formaldehyde, and polyvinyl pyrrolidone (note H. Freytag, Ullmanns Encyclope dia of Technical Chemistry, 3rd Edition, vol. 10, pages In more recent times there has also been provided mixed polymerizates of N-substituted acrylic acid amides with unsaturated carboxylic acid derivatives (German Auslegeschrift No. 1,091,290), homo-polymerizates or mixed polymerizates of acrylic acid esters (German Auslegeschrift No. 1,015,193), which after lpolymerization are saponied until wa-ter solubility, as well as mixed polymerizates of basic esters of unsaturated carboxylic acids with N-substituted acrylic acid amides and ethylenic unsaturated compounds (German Auslegeschrift No, 1,095,467), and finally mixed polymerizates of N-vinylpyrrolidone with vinyl esters (German Auslegeschrift No. 1,089,930).

Both methods, however, have the disadvantage that the hair deformation which is accomplished by the mentioned agents results in an undesirable alteration when there is a relative humidity in the air of more than about 5060%. While in the case of the irst method the deformed hair, depending upon the type of treatment and the hair structure, is drawn together like a corkscrew or becomes strand-like and shapeless (i.e., the hair is either curled or straightened) hair treated with resins or synthetic emulsions or solutions will have only the last mentioned disadvantage. The named hair deformation agents consequently only are useful and hold their stability at relatively low humidity. Y

With some lof these agents, in certain cases a protective effect against water is obtained, however not against water vapor. In practice the stability against water is of lesser importance while the protection against water vapor is of considerable importance in maintaining a permanent hair setting. A known example of the sensitivity of human hair to atmospheric moisture is its use in hygrometers.

It is known that the relative humidity may in general achieve values between 70 and 90%, `and particularly in the morning and evening hours, as well as in the kitchen and bathrooms the value may go up to 100%. In order to achieve a satisfactory protection against such high humidityconditions it is necessary with the known filmforming agents to provide a layer which is actually several times thicker than the diameter of the hair iibers themselves. This is of course not possible because it would ice change the properties of the hair, particularly the combability and the feel of the hair.

In general it can be stated that all attempts at reducing the hygroscopicity of the'hair and increasing the stability of the hair setting against atmospheric moisture have, for all practical purposes, been unsuccessful.

It is accordingly a .primary object of the present invention to provide for the treatment of hair with compositions which fully protect the hair against high humidity.

It is another object of the present invention to provide for the protection of hair against high humidity so that a hair setting remains stable for long periods of time and even under conditions of high humidity whereby the additional advantage is obtained that the combability and feel of the hair remain as though the hair were untreated.

It is yet another object of the present invention to provide a method of setting hair and compositions for such purpose which result in the formation of stable hair settings even under conditions of relative humidity.

In accordance with yet another object of the present invention hair, prior to setting, is moistened with a solution or emulsion which has the property of protecting hair against atmospheric humidity so that when the set hair is dried it will remain in the desired set condition over a long period of time and even under conditions -of high humidity. Furthermore, in accordance with the present invention, the thus treated hair remains soft and natural to the touch.

Other objects and advantages of the present invention will be apparent from a further reading of the specification and of the appended claims.

With the above and other objects in view, the present invention mainly comprises the application to hair of at least lone compound having at least two epoxy groups per molecule and at least one substance which is adapted to react with and harden the compound, whereby the reaction product of the compound and the substance has the property of maintaining the hair in set condition over a relatively long period of time and even in moist atmospheric conditions.

As will be more fully described below the hair may be treated with a solution of the poly-epoxy compound and with a solution of the hardener, which, for example, may be a polyamine or a polycarboxylic acid, so as to wet the hair, the hair then being set in normal manner in wet condition,'for example by being wound around rollers or curlers or the like, whereupon the hair is then dried. The resulting hair will remain in set condition even under conditions of extremely high relative humidity.

It has surprisingly been found that in contrast to the artificial substances which have been used prior to the present invention hair which has been treated with the so-called epoxy resins is not sensitive to humidity. While in the case of allknown methods, without exception, the products which were used, simply rby drying of the applied solution or emulsion would form the film, in accordance with the method of the present invention the lm coating the hair is iirst formed by chemical reaction between the epoxy compound and the used hardener on the hair.

Furthermore, since all known film formers were applied either in the form of solutions in water, in Water-alcohol mixtures or in alcohol, or in the form of emulsions made by means of hydrophilic emulsifying agents, this being the only possible manner of bringing the same onto the hair, the resulting lm which was formed on the hair was naturally hydrophilic and consequently easily permeable by water vapor. Contrary thereto, in accordance with the present invention, despite the good water solubility, or solubility in solvents which are miscible with water, of the starting components, the film which is formed by the reaction of the starting compone-nts is a strongly three dimensional cross linked compound which is practically cause a portion of the epoxy groups react with reactable l amino gnoups or hydroxyl groups of the hair kenatin. Consequently, when human hair is treated in accordance with the method of the present invention, the obtained treated hair is remarkably resistant even to relative humidity of 90100%. In addition, certain properties of the hair, in contrast to the action of the previously mentioned deformation agents, are favorably changed by means of the present invention. Thus, by a treatment Iin accordance with the method of the present invention, the so-called nitrogen number (note H. Freytag, Characterization of Sulfur-Containing Proteins, Folia Pharmaceutica (Istanbul), 3, 7:125-141 (1955)) which in the case of cosmetically untreated hair is markedly reduced, is considerably reduced in the case of hair which is permanently waved. This nitrogen number is a measure of the number of free SH-groups in the keratin and thereby ofthe degree of cross linking. Thus, for example, in the case of hair whichhas been treated with the usual reducing agen-ts such as substituted mercaptans, in order to permanently wave the same, the number of free SH-groups of the keratin is a measure of the degree of damage because, despite fixing, only a portion of the disulfide bridges which have been split by the reduction are reformed. By hair deformation in accordance with the present invention the number of SH- groups is, contrary to the other permanent waving methods, not increased, but is actually decreased. It may be considered that the reduction of the nitrogen number is partially due to the coating by means of the epox-ide resin lm.

' The preferred polyepoxy starting compounds of the present invention are preferably those compounds having at least two epoxy groups per molecule which are soluble in Water or in mixtures of Water and Water-miscible solvents or in water-miscible solvents, such as:

Ethylene glycol diglycidyl ether CH2-O O Hz-C H Q H2 CH20*C Hz-C H-C H2 1,3-butane diol diglycidyl ether CHT-O o Hz-C H--C H2 CH2 O CH-O-CHn-C H C H2 CH3 O 1,4-butane diol digly-c-idyl ether CH2-O o Etz-C {1 -C H,

1-e'DoXyethyl-3,4-epoxycyclohexane CH-CHz Y 4 3,4-epoxy-6-rnethyl-cyclohexylmethyl-3,4-epoxy-6 methyl-cyclohexane carboxylate CHz-O-C O C H3 H3G Dicyclopentadiene di-epoxide l\-l; C O

Butadiene di-epoxide Triglycidyl-ether of the reaction product of glycerine and four moles ethylene oxide.

Tetraglycidyl-ether of the reaction product of pentaerythritol and four moles ethylene oxide. Y

or mixtures thereof. All of these compounds are commercially available and can be produced according to conventional methods either from epichlorohydrin (a typical method of production is shown in Example 1) or by epoxidation of polyunsaturated compounds (for example according to the method of Prileschajew, in Ber. 42, 4811 (1909) or Arbusow and Michailow, J. pr. Chem. 127, 97 1930) The hardeners which are used, i.e., the substances which react with and harden the polyepoxy compound, such as polyamines and polycarboxylic acids, are preferably also those which are soluble in water, or in mixtures of Water and water-miscible solvents, or in the Water-miscible solvents themselves. Among the suitable soluble primary or secondary diamines or polyamines are: ethylene diamine, diethylenetriamine, dipropylenetriamine, the above being unsubstituted polyamines, and also suitable are suhstituted aliphatic or aromatic diamino compounds which contain mainly carboxyl or hydroxyl groups, such as 3,4-

diaminobenzoic acid, lysine, ornithine, arginine, cystine, N,N'-bis-oxyethyl-ethylenediamine, and the like. Among the particularly suitable hardeners are those hydroxylgroup-containing diamines which are obtained by the reaction of a compound containing at least two epoxy groups, suchas those mentioned above, with ammonia. The compound resulting from such reaction is a particularly suitable hardener for the purposesof the present invention.

Also suitable or other bifunctional compounds such as polycarboxylic acid, e.g., maleic acid', which is preferably used in the form of its anhydride, adipic acid and the like, as well as other bifunctional compounds such as compounds which contain both an amino group and a mercapto group, e.g., cysteamine (HS-CH2-CH2NH2) or cysteine.

In accordance with the present invention the hair is treated with a solution, which is preferably formed shortly before use, containing both at least one -compound having at least two epoxy groups per molecule and at least one hardener therefor. The ratio of the epoxy compound to the hardener may be varied within extremely wide limits, but is most preferably chosen so that for each epoxy group there is present about one reactable hydrogen atom of the hardener. The thus formed solution can be applied to the hair in usual manner. For example a relatively dilute solution of the so-called setting lotion or finger wave lotion can be applied and without removal of the excess can be permitted to react under the drier. It is also possible to rst permit a concentrated solution to work in for several minutes, the excess to then be removed by rubbing or rinsing, and then setting the hair and permitting it to dry under the dryer. Itis also possible to operate according to a two stage method wherein the epoxy ycomponent is first permitted to work in for several minutes, the excess removed and then the hardener applied to the hair which is then set and dried. Likewise, it is of course possible to work in the reverse manner, i.e., to iirst apply the hardener, then to apply the epoxy, then to set the hair and dry it.

It is also possible in accordance With the present invention to add to the epoxy-hardener-system an accelerator and/ or other agents which can vary the properties of the obtained resin so as to improve the same. Particularly suitable for this purpose may be mentioned resorcinol, catalytic amounts of heavy metal salts, particularly copper salts, thiosemicarbazides, and cationic active wetting agents such as cetyl pyridinium chloride.

The following examples are given to further illustrate the present invention. The scope of the invention is not, however, meant to be limited to the specic details of the examples.

EXAMPLE 1 Solution A 17.4 g. of ethylene glycol diglycidyl ether are dissolved in water and the amount of the solution adjusted to a total of 100 cc. The ethylene glycol diglycidyl ether can be produced, for example, in accordance with the following method:

0.5 mols of ethylene glycol are mixed with 2.5 mols of epichlorohydrin. Into this mixture is stirred 1 mol of potassium hydroxide, in small portions, while maintaining the temperature of the reaction mixture below 35 C. After the completion of the introduction of the potassium hydroxide the reaction mixture is stirred for two hours at room temperature, vthe formed potassium chloride is then filtered off, the filtrate dried with dry sodium sulfate, and the excess of epichlorohydrin distilled off under vacuum. The remaining residue is purified by distillation at a pressure of about 0.3 mm. Hg. There is thus obtained a product, which upon analysis is found to have a degree of purity of about 95%, calculated with respect to the ethylene glycol diglycidyl ether.

Solution B 13.1g. of dipropylenetriamine are dissolved in water and the solution brought `to a volume of cc.

30 cc. of solution A are mixed with 20 cc. of solution B. Hair is then treated with the necessary amount of this solution and the solution is permitted to work` into the hair for about 15 minutes. The hair is then wiped dry with the usual paper towels used in beau-ty parlors, wound upon rollers in the usual manner and under a drier is dried at a temperature of 40-50 C. for `about 15 to 45 minutes, depending upon the fullness of the hair. After combing out there is obtained a stable setting which is practically completely insensitive to high humidity. In addition the air has a particularly nice gloss.

EXAtMPLE 2 A solution A is prepared as in Example 1.

Solution B 13.1 g. of dipropylenetriamine are dissolved in water, the solution diluted to 100 cc. and 3 g. of resorcinol are added thereto.

The further treatment proceeds as described in Example l.

Treatment with this composition lresults in the setting which is still more stable to atmospheric moisture than in the case of Example 1.

EXAMPLE 3 A solution A is prepared as in Example 1.

Solution B To the solution B o-f either Example 1 or Example 2 is added 0.5 g. of cetylpyridinium chloride. The use of this solution is facilitated because of the increased wetting power thereof, and the hardening is surprisingly consider-ably accelerated.

EXAMPLE 4 A solution A is prepared as in Example 1.

Solution B 10.3 g. of diethylenetriamine are dissolvedrin Water and the solution diluted to a Volume of 100 cc. The further treatment proceeds as described in Example 1.

EXAMPLE 5 Solution A 20.2 g. of 1,4-butanedioldiglycidyl ether are/dissolved in water and the volume brought to 100 cc.

A solution B is prepared in accordance with Example 2, solution A is mixed with solution B and the further treatment is as described in Example 1.

EXAMPLE 6 A solution A is prepared as in Example 1.

Solution B 17.4 g. of ethylene glycol diglycidyl ether are mixed with 75 cc. of 25% aqueous ammonia solution and with water the volume is brought to a total of 100 cc. After a short time the solution becomes considerably warmed, and then the reaction mixture is maintained at a temperature of about 45-55 C. for 1 hour. The excess ammonia is then distilled off by steam and the remaining solution, after cooling with water, is diluted to a volume of 100 cc.

Solution A is mixed with 30 cc. of solution B and then the further procedure is as described in Example 1. The setting obtained with this composition is still more stable against humidity than in the case of the setting obtained according to Example 1.

EXAMPLE 7 The same conditions as in Example 6 are used for making the hair treating composition, except that the final composition is prepared from 20 cc. of solution A, 20 cc. of solution B and 2O cc. of Water.

EXAMPLE 8 20 cc. of solution B of Example 2 are -iirst applied to the hair, and after about minutes the hair is wiped fairly dry. The hair is then treated in the same manner with 20 cc. of solution A of Example 2 and the hair thus treated is Vthen dried for 30 minutes under a drier at a temperature of about 40-50" C. After combing out the set-ting which is obtained is quite analogous with respect to its resistance against moisture to that obtained according to Example 2.

EXAMPLE 9 Solution A 13.9 g. of l-epoxyethyl3,4-epoxycyclohexane are dissolved in 50 cc. of isopropyl alcohol and the solution is diluted to a volume of 100 cc. with water. l

A solution B is prepared as in Example 1 and the lfurther working up proceeds as in Example 1.

EXAMPLE 10 Solution A 20.4 g. of glycerine diglycidyl ether are dissolved in Water and the volume of the solution brought to 100 cc.

A solution B is prepared as in Example 2 and the further treatment proceeds as in Example 1.

Solution B is prepared as in Example 2, and further procedure is as described in Example 1.

s EXAMPLE 13 A solution A is prepared as in Example l.

Solution B 13.1 g. of dlpropylenetriamine are dissolved in Water, l() cc. of concentrated ammonia are added thereto and also added is 0.001 g. of C-uSO-5H2O and then the solution is diluted to a-volume of 100 cc. with Water. The further procedure is as described in Example l.

EXAMPLE 14 A solution A is prepared as in Example l.

Solution B 13.1 g. of dipropylenetriamine are dissolved in water, the solution is brought t-o a volume of 100 cc, and 3 g. of thiosemicarbazide are added thereto. The further procedure is as described in Example 1.

EXAMPLE 15 A solution A is prepared as in Example 1.

Solution B 15.2. g. of 3,4-diam-inobenzoic acid are dissolved in S0 cc. of isopropyl alcohol, 10 cc. of concentrated ammonia are added thereto and the solution is diluted to 100 cc. with Water. The further procedure is as described in Example 1.

' EXAMPLE 16 I A solution A is prepared as in Example 1.

Solution B 24 g. of cystine and 8 g. of sodium'hydroxide are diluted in water and the volume brought to 10() cc. The solutions A and B are mixed in a ratio of 1:1.

The further procedure is as .described in`Example l.

v EXAMPLE 17 A solution A is prepared as described in Example 9.

Solution B 9.8 g. of maleic acid anhydride are dissolved in Water and the solution brought to a volume of 100 cc.

The solutions A and B are mixed in proportions of 1:1 and further procedure is as described in Example 1.

EXAMPLE 18 A solution A is prepared according to Example l.

Solution B 7.8 g. of ethylenediamine-monohydrate are dissolved in Water and the solution brought to a volume of 100 cc. with water. The solutions A and B are mixed in proportions of 1:1.

The further procedure is as described in Example 1.

EXAMPLE 19 A solution A is prepared as in Example 12.

Solution B 14.6 g. of adipic acid are dissolved in 60 cc. of isopropyl alcohol and the volume of the solution is brought to 100 cc. with water. The solutions A and B are mixed in proportions of 1:1. The further procedure is as described in Example l.

EXAMPLE 20 A solution A is prepared as in Example 1.

Solution B is prepared as in Example 1.

30 cc. of solution A are mixed with 20 ec. of solution B. 'Ihis mixture is then diluted With 25 ec. or with 50 cc. or with 75 cc. of water, applied to the hair in the usual manner and the hair is then dried. Even with these dilute solutions very stable settings are obtained. Even in the case of the most dilute solution a very stable setting is obtained.

EXAMPLE 21 X grams of one of the following epoxides and Y grams of dipropylenetriamine are dissolved in Water up to a total of 100 c-c. and applied to the hair according to Example 1:

' Dipropylene- Epoxide X, g.: triamine Y, g. 21.1 Di-glycol-di-glycidyl ether, or 7.15 19.6 Tri-glycol-di-glycidyl-ether, or 20.8 Tetra-glycol-di-glycidyl-ether, or

6.5 5.8 20.8 Polyglycol-ZOO-di-glycidylether,or 5.8

22.7 Polyglycol-3(lO-di-glycidyl-ether, or 4.8 24.1 Polyglycol-400-di-glycidyl-ether, or 3.9 25.0 Polyglycol-GOO-di-glycidyl-ether, or 3.3 17.4 Triglycidyl-ether of the reaction product of glycerne and four moles ethylene oxide,

or 8.3 25.2 Tetraglycidyl-ether of the reaction product of pentaerythritol and four moles ethylene oxide, or 3.16 21.1 Triglycidyl cyanurate v 5.8

After combing out, the hair has obtained a stable setting which is practically completely insensitive to high humidity.

10.0 g. triglycidylcyanurate and one of the following amines are dissolved in water up to a total of 100` cc.

' and applied to the hair according to Example 1:

(a) 3.35 g. N-aminoethyl-N-hydroxyethylamine (b) 3.8 g. N-hydroxyethyl-1,3-propanediamine (c) 3.8 g. N-Z-hydroxypropyl-ethylenediamine (d) 5.6 g. N,Ndi2-hydroxypropyl-ethylenediamine (e) 4.75 g. N,Ndi-hydroxyethyl-ethylenediamine The hair treated with one of these hardeners has obtained a stable setting, which is practically completely insensitive to high humidity.

The following is a description of comparative tests carried out to determine the properties of hair treated in accordance with the present invention as compared to other methods.

To compare the hair protecting action obtained according to the method of the present invention the nitrogen number was determined in accordance with the method of H. Freytag (see above) of hair treated in accordance with the method of the present invention in comparison to hair treated with the usual permanent waving compositions based on thioglycolates:

Cosmetically untreated hair was treated with the composition of Example 2.

The nitrogen number, which for the untreated hair was 2.4, was reduced to 1.45.

In comparison thereto, hair subjected to permanent waving in the usual manner with ammoniacal thioglycolate solution and subsequently xed resulted in the hair having a nitrogen number of 18.7. This hair when treated with the composition of Example 2 resulted in the nitrogen number thereof being reduced to 12.9.

The proof of the technical advance made by the method of the present invention in the'eld o-f hair setting as compared to known methods is apparent from the herewith submitted graphs which show the increase in a length of hair strands waved in accordance with the method of the present invention and in accordance with known methods, in centimeters, at relative humidities of approximately 30, 50, 70 and 95% at a temperature of 20 C. The diameter of the hair curler was mm., the length of the uncurled hair strand 18 cm., and the weight of the hair strand 1.0 g. The starting length of the curled and combed strands before introduction into the moisture chamber was about 3 cm. The values shown in the graphs indicate the effective increase in length, omitting the initial 3 cm. length.

In the graphs the curls I, II, III and IV designate hair treated with the composition indicated below, in all cases the hair being wetted with the composition, wound on curlers, and dried under' a drier at a temperature of about 50 C. for 30 minutes.

I.=composition of Example l, application to hair which has not previously been treated,

Il.=composition of Example 6, application to hair which has not previously been treated,

III.=water, applied to hair which has been permanently waved in the usual manner with ammonium thioglycolate solutions, and

IV .=compositions base-d on the use of prior known agents which were applied to hair which had not previously been treated. All of the tested substances gave practically the same values and it is for this reason that the values are all set forth in the one curve IV. The following agents were tested:

(a) water;

(b) 2% aqueous solution of hydroxy ethylcellulose;

(c) 2% solution of polyvinyl pyrrolidone in a mixture of equal parts of water and isopropyl alcohol;

(d) 2% solution of vinyl pyrrolidone-vinylacetate mixed polymerizate (proportion of 30:70) in waterisopropanol mixture of equal parts of water and isopropanol;

(e) 2 g. shellac in 40 cc. of water are brought to a pH value of 8 by the addition of aqueous ammonia, mixed with 49 g. of isopropanol and diluted with water to 100g.;

(f) 1 g. of polymethacrylic acid (Rohagit S, middle viscosity, produced by Rohm and Haas G.m.b.H.,

t@ Darmstadt, Germany) in cc. of water are brought to a pH value of S by means of aqueous ammonia and diluted with water to 1GO g.

Curves I and II indicate the stability against moisture of hair curled in accordance with the present invention, while curves III and IV in-dic-ate the stability for hair curled -in accordance with the prior art. The points given in the graphs which are used for the curves are average values, each taken for 5 separate measurements. From the curves it is apparent that all known coating agents lack resistance in similar manner, that a considerable improvement is obtained by treatment of the hair with permanent waving compositions based on the use of mercaptans, while in all cases hair treated in accordance with the present linvention is considerably more resistant to the action of humidity.

Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily `adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to ybe secured lby Letters Patent is:

1. Method of maintaining hair in set condition, which comprises wetting hair with a solution containing at least one compound compatible with hair and having lbetween two and four terminal epoxy groups per molecule wherein the epoxy group is of the structure and at least one substance adapted to react with and harden said compound, dissolved in a solvent therefor selected from the group consistingof water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and said substance,- whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

2. Method of maintaining hair in set condition, which comprises wetting hair with la solution of at least one compound compatible with hair and having between two and four terminal epoxy groups per molecule wherein the epoxy group is of the structure and at least one substance selected from the group consisting of primary and secondary diamines and triamines adapted to react with and harden said compound, dissolved in a solvent therefor selected from the group consisting of water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and said substance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

3. Method of maintaining hair in set condition, whichcomprises wetting hair with an aqueous solution containing at least one compound compatible with hair and having between two and four terminal epoxy groups per molecule wherein the epoxy group is of the structure I C*C \O/ and at least one substance adapted lt-o react with and harden said compound; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and said subst-ance, whereby the l l hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions,

4. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound being selected from the group consisting of ethylene glycol diglycidyl ether, 1,3-butanedio1 diglycidyl ether, 1,4-butanediol diglycidyl ether, glycerine diglycidyl ether, 1-epoxyethyl-3,4-epoxycyclohexane, 3,4-epoxy-6- methyl cyclohexylmethyl 3,4epoxy6'methylcyclohexane carboxylate, dicyclopentadienediepoxide, butadienediepoxide, diglycidyl ether, polyglycohdiglycidylether, triglycidyl-ether of the reaction product of glycerine and four moles ethylene oxide, tetraglycidylether of the reaction product of pentaerythritol and four moles ethylene oxide, and triglycidyl cyanurate and at least one substance adapted to react with and harden said compound, dissolved in a solvent therefor s elected from the .group consisting of water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby Vcausing reaction between said compound and said substance, whereby the hair -will remain in set condition over a relatively long period of time .and even under moist atmospheric conditions.

5. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound being selected Vfrom the group consisting of ethylene glycol diglycidyl ether, l,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, glycerine diglycidyl ether, 1-epoxyethyl3,l-epoxycyclohexane, 3,4-epoxy-6 methyl cyclohexylmethyl 3,4epoxy-6'methylcyclo hex-ane carboxylate, -dicyclopentadienediepoxide, butadienediepoxide, diglycidyl ether, polyglycol-diglycidylether, triglycidyl-ether of the reaction product of glycerine and four moles ethylene oxide, tetraglycidyl-ether of the reaction product of pentaerythritol and tour moles ethylene oxide, and triglycidyl cyanurate and at least one substance adapted to react with and harden said cornpound and being selected from the group consisting of ethylenediaminc, diethylenetriamine, dipropylenetri* amine, lysine, 3,4-diaminobenzoic acid, ornithine, arginine, cystine, N,N bis oxyethyl-ethylenediamine, cysteamine, Naminoethyl-N-hydroxyethylamine, N-hydroxyethyl 1,3 propanediamine, N-2hydroxypropyl ethylenediamine, N,N di-Z-hydroxypropyl-ethylenediamine, N,N' di-hydroxyethyl-ethylenediamine, cysteine, maleic acid, adipic acid and the reaction product of ethylene glycol diglycidyl ether with ammonia, dissolved in a solvent therefor selected from the group consisting of water, water miscible solvents and mixtures thereof;

setting the thus wetted hair; and drying the thus set hair,

thereby causing reaction between said compound and said substance, whereby the hair will remain in set condition over -a relatively long period of time and even under moist atmospheric conditions.

6. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound compatible with hair and having between two and four terminal epoxy groups per molecule wherein the epoxy group is of the structure and at least lone reaction product of said compound with ammonia, said reaction product being adapted to react with and harden said compound, dissolved in a solvent therefor selected from the group consisting of water, water misci-ble solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and said sub-- stance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions` '7. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound compatible with hair and having between two and four terminal epoxy groups per molecule wherein the epoxy group is of the structure and at least one substance selected from the group consisting of cysteamine and cysteine and being adapted to react with and harden said compound, dissolved in a solvent therefor selected from the group consisting of water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and Said substance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

8. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound having between two and four epoxy groups per molecule and `being selected from the group consisting of ethylene glycol diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, glycerine diglycidyl ether, l-epoxyethyl-3,ll-epoxycyclohexane, 3,4- epoxy -methylcyclohexylmethyl-3,4'epoxy6methyl cyclohexane carboxylate, dicyclopentadienediepoxide, butadienediepoxide, diglycidyl ether, polyglycol-diglycidylether, -triglycidyl-ether of the reaction product of glycer'me and four moles ethylene oxide, tetraglycidylether of the reaction product of pentaerythritol and four moles ethylene oxide and triglycidyl cyanurate, and at least one substance adapted to react with and harden said compound and being selected from the group consisting of ethylenediamine, diethylenetriamine, dipropylenetriamine, lysine, 3,4diaminobenzoic acid, ornithine,

arginine, cystine, N,N'-bis-oxyethyl-ethylene-diarnine, N-aminoethyl-N-hydroxyethyl-amine, N hydroxyethyl 1,3 propanediamine, N 2 hydroxypropyl-ethylenediamine, N,Ndi2hydroxypropy1ethylenediamine, N,N di-hydroxyethyl-ethylenediamine, cystehmine, cysteine,- maleic acid, adipic acid and the reaction product of said compound with ammonia, yand also containing in solution thiosemicarbazide as a material adapted to accelerate the reaction lbetween said compound and said substance, dissolved in a solvent therefor selected from the group consisting of water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and said substance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

9. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound compatible with hair and having between two and four terminal epoxy groups per molecule wherein the epoxy group is of the structure and at least one substance adapted to react with and harden said compound and also containing resorcinol, dissolved in a solvent therefor selected from the group consisting of water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and said substance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

10. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound having between 2 and 4 epoxy groups per molecule and being selected from the group consisting of ethylene glycol, diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, glycerine diglycidyl lepoxyethyl,ll-epoxycyciohexane, r:lA-epoxy- 6 methyl-cyclohexylmethyl-3,4-epoxy-6'-methyl-cyclohexane carboxylate, dicyclopentadienediepoxide, butadienediepoxide, diglycidyl ether, polyglycol-diglycidylether, t-riglycidyl-ether of the reaction product of glycerine and four moles ethylene oxide, tetraglycidyl-ether of the reaction product of pentaerythritol and four moles ethylene oxide and triglycidyl cyanurate, and at least one substances adapted to react with and harden said compound and being selected from the group consisting of ethylenediamine, diethylenetriamine, dipropylenetriamine, lysine, 3,4-diaminobenzoic acid, ornithine, arginine, cystine, N,N'-bis-oxyethyl-ethylenediamine,l N- aminoethyl-N-hydroxyethyl-amine, N-hydroxyethyl-1,3 propanediamine, N 2 hydroxypropyl-ethylenediamine, N,N-di-2-hydroxypropylethylenediamine, N,N di-hydroxyethyl-ethylene-diamine, cysteamine, cysteine, maleic acid, adipic acid and the reaction product of said compound with ammonia, dissolved in a solvent therefor selected from the group consisting of water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction between said compound and said substance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

11. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound having between 2 and 4 epoxy groups per molecule and being selected from the group consisting of ethylene glycol, diglycidyl ether, 1,3-'butanediol diglycidyl ether, 1,4-butane-diol diglycidyl ether, glycerine diglycidyl ether, l-epoxyethyl-3,4-epoxycyclohexane, 3,4- epoxy 6-methyl-cyclohexylmethyl-3,4'epoxy6methylcyclohexane carboxylate, dicyclopentadienediepoxide, butadienediepoxide, diglycidyl ether, polyglycol-diglycidyl ether, triglycidyl-ether of the reaction product of glycerine and four moles ethylene oxide, tetraglycidylether of the reaction product of pentaerythritol and four moles ethylene oxide and triglycidyl cyanurate, and at least one substance adapted to react with and harden said compound and also containing in solution a material selected from the group consisting of resorcinol, thiosemicarbazides, cetyl pyridinium chloride, and catalytic Y amounts of a copper salt, dissolved in a solvent therefor selected from the group consisting of water, Water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying the thus set hair, thereby causing reaction Ibetween said compound and said substance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

12. Method of maintaining hair in set condition, which comprises wetting hair with a solution of at least one compound having between 2 and 4 epoxy groups per molecule and being selected from `the group consisting of ethylene glycol, diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4Jbutanediol diglycidyl ether, glycerine diglycidyl ether, 1-epoxyethyl-3,4-epoxycyclohexane, 3,4- epoxy -methyl-cyclohexylmethyl-3,4epoxy6methylcyclohexane carboxylate, dicyclopentadienediepoxide, butadienediepoxide, diglycidyl ether, polyglylcol-diglycidyl-ether, triglycidyl-ether of the reaction product of glycerine and four moles ethylene oxide and triglycidyl cyanurate, and at least one substance adapted to react with and harden said compound and also containing in solution a material selected from the group consisting of resorcinol, thiosemicarbazides, cetyl pyridinium chloride,

and catalytic amounts of a copper salt, dissolved in a solvent therefor selected from the group consisting of water, water miscible solvents and mixtures thereof; setting the thus wetted hair; and drying `the thus set hair, thereby causing reaction between said compound and said substance, whereby the hair will remain in set condition over a relatively long period of time and even under moist atmospheric conditions.

References Cited by the Examiner UNITED STATES PATENTS 2,070,990 2/ 1937 Groll et a1. 260-47 2,510,885 6/1950 Greenlee 260-47 2,585,115 2/1952 Greenlee 260-47 3,052,650 9/1962 Wear 260--47 OTHER REFERENCES Hackhs Chemical Dictionary, The Blakeston Co., Philadelphia (1944), p. 310.

Noller: Chemistry of Organic Compounds, W. B. Saunders Co., Philadelphia (1957) pp. 750-751.

JULIAN S. LEVITT, Primary Examiner.

FRANK CACCIAPAGLIA, Examiner.

VERA C. CLARKE, Assistant Examiner. 

12. METHOD OF MAINTAINING HAIR IN SET CONDITION, WHICH COMPRISES WETTING HAIR WITH A SOLUTION OF AT LEAST ONE COMPOUND HAVING BETWEEN 2 AND 4 EPOXY GROUPS PER MOLECULAR AND BEING SELECTED FROM THE GROUP CONSISTING OF ETHYLENE GLYCOL, DIGLYCIDYL ETHER, 1,3-BUTANEDIOL DIGLYCIDYL ETHER, 1,4-BUTANEDIOL DIGLYCIDYL ETHER, GLYCERINE DIGLYCIDYL ETHER, 1-EPOXYETHYL-3,4-EPOXYCYCLOHEXANE, 3,4EPOXY - 6-METHYL-CYCLOHEXYLETHYL-3,4''-EPOXY-6''-METHYLCYCLOHEXANE CARBOXYLATE, DICYCLOPENTADIENEDIEPOXIDE, BUTADIENEDIEPOXIDE, DIGLYCIDYL ETHER, POLYGLYLCOL-DIGLYCIDYL-ETHER, TRIGLYCIDYL-ETHER OF THE REACTION PRODUCT OF GLYCERINE AND FOUR MOLES ETHYLENE OXIDE AND TRIGLYCIDYL CYANURATE, AND AT LEAST ONE SUBSTANCE ADAPTED TO REACT WITH AND HARDEN SAID COMPOUND AND ALSO CONTAINING IN SOLUTION A MATERIAL SELECTED FROM THE GROUP CONSISTING OF RESORCINOL, THIOSEMICARBAZIDES, CETYL PYRIDINIUM CHLORIDE, AND CATALYTIC AMOUNTS OF A COPPER SALT, DISSOLVED IN A SOLVENT THEREFOR SELECTED FROM THE GROUP CONSISTING OF WATER, WATER MISCIBLE SOLVENTS AND MIXTURES THEREOF; SETTING THE THUS WETTED HAIR; AND DRYING THE THUS SET HAIR, THEREBY CAUSING REACTION BETWEEN SAID COMPOUND AND SAID SUBSTANCE, WHEREBY THE HAIR WILL REMAIN IN SET CONDITION OVER A RELATIVELY LONG PERIOD OF TIME AND EVEN UNDER MOIST ATMOSPHERIC CONDITIONS. 